CA2146012A1 - Supported homogenous catalyst complexes for olefin polymerization - Google Patents

Abstract

A supported catalyst complex having a Group 4 metal cyclopentadienyl derivative and an aluminoxane reacted with silica which show improved resistance to catalyst poisoning. The supported catalyst composition is particularly suitable for producing homogeneous ethylene polymers and copolymers having a narrow molecular weight distribution. The invention further includes the process of preparing the supported catalyst compositions and their use as olefin polymerization catalysts. The catalyst sup-port is prepared by contacting silica with an aluminoxane, preferably either methylaluminoxane or modified methylaluminoxane.

Description

2 1 4 6 0 1 2 PCr/US93/09377 SUPPORTED HOMOGENEOUS CATALYST COMPLEXES FOR
OLEFIN POLYMERIZATION

BACKGROUND OF THE INVENTION
Field of the Invention The invention relates to compositions of matter which are useful as supported homogeneous catalysts for vinyl addition polymerization, as well as methods for preparing these catalysts, and a process of polymerizing alpha-olefins using these catalysts. More particularly, the invention relates to a supported, three-component homogeneous catalyst useful for making ethylene polymers and copolymers.

Technolo~y Review The modern methods of catalyzing the polymerization of alpha-olefins using a transition metal catalyst were first generally described by Ziegler, Natta and by researchers at Phillips Petroleum. Although highly improved polymerization methods have been developed over the course of time, these catalysts still produce heterogeneous type polymers; that is, the polymeri7~tion reaction product is a complex mixture of polymers, with a relatively wide distribution of molecular weights. This wide distribution of molecular weights has an effect (generally detrimental) on the physical properties of the polymers.

The molecular weight distribution (MWD), or polydispersity, is a known variable in polymers which is described as the ratio of weight average molecularweight (Mw) to number average molecular weight (Mn) (i.e., Mw/Mn), parameters which can be measured directly, for example by gel permeation chromatography ~14~2 WO 94/07928 PCr/US93J09377 techniques. The MWD can also be approximated by the Ilo/I2 ratio, as described in ASTM D-1238. The Ilo/I2 ratio is also an indicator of the shear sensitivity and processibility for ethylene polymers. Low density polyethylenes (LDPE) typicallyhave a higher Ilo/I2 ratio than linear low density polyethylenes (LLDPE) or ultra S low density polyethylenes (ULDPE) and are easier to melt process in f~bric~tion equipment.

Recently, ethylene polymers having a narrow MWD were introduced.
These polymers were produced using a so-called "single site catalyst."
In EP 0 416 815, published March 13th, 1991, there are disclosed certain constrained geometry complexes comprising a strain-inducing delocali_ed pi-bonded moiety and metals of Groups 4 to 10 of the Periodic Table of the Elements.
Such compositions formed catalysts in the presence of activating cocatalysts such as methylaluminoxane, all-minllm aL~yls, aluminum halides, ~lllminllm alkylhalides, Lewis acids, ammonium salts, non-interfering oxidi7ing agents, andmixtures of the foregoing.

In U.S. Patent Nos. 5,026,798 and 5,055,438, certain Group 4 met~llocene compounds having a heteroatom ligand were also used in combination with aluminoxanes as olefin polymeri7~tion catalysts.

In EP 0 418 044, published March 29th, 1991), certain cationic derivatives of the foregoing constrained geome~y catalysts are disclosed as olefin polymeri7~tion catalysts. These cationic catalysts have excellent catalytic activity but unfortunately they are undesirably sensitive to polar impurities contained in the WO 94/07928 2 1 4 6 0 1 2 PCr/US93/09377 olefin monomers, the polymerization mixture, or even the polymeri7~tion reactor which act as catalyst poisons. When the polar impurities are present, the catalyst lifetimes have been limited and the molecular weights of the resulting polymers have been reduced. Thus, special handling is required to elimin~te such polar impurities.

Trialkylboron, triaL~ylah-minl-m and ~h-minQxane compounds have been employed to remove catalyst poisons from biscyclopent~-lienyl-containing olefin polymerization catalysts. Such adjuvants have proven to be ineffective in combating the inhibition or poisoning of the cationic catalysts and they may actually interfere with the desired catalytic polymerization process. For example, in J. Am.
Chem. Soc. 113. 8570-8571 (1991), it has been reported that the use of minoxanes in combination with biscyclopent~ienyl-containing cationic olefin polymeri7~tion catalysts results in the detrimental interference with the catalyst for propylene polym~ri7~tions. Catalyst poisoning is a problem, particularly for cationic catalysts.

Accordingly, there is a need for new or improved organomet~llic catalyst compositions, particularly supported homogeneous catalyst compositions, that (1)are l~si~.Lanl to the effects of polar impurities and other catalyst poisons, and that (2) have extended catalyst lifetimes and improved polymPri7~tion efficiencif s Additionally, there is a need for new or improved organometallic catalyst compositions, particularly homogeneous catalyst compositions, which can be used in either gas-phase olefin polymeri7~tion reactions, slurry olefin polymeri7~tion reactions or solution olefin polymeri7~tion reactions. The cationic catalysts are W094/07928 2~ ~6~1~ PCr/US93/09377 known to be quite useful in solution polymerizations but are generally considered less useful in slurry polymerizations, and of even less value in gas-phase polymerizations .

Various techniques have been tried to overcome the low polymerization activities of the catalysts. For example, alkylaluminoxane cocatalysts were inc-luded in molar ratios of greater than 500: 1 relative to the organompt~ c catalyst species (Chien, et al., J. Pol. Sci.. Part A, 26, 2639,(1987)). Others have tried drastic polymerization conditions (e.g., very high reaction pressures) to improve polymerization rates and efficiencies. Such efforts are illustrated in EP O 260 999. In WO 91/09882, published July 11th, 1991, it has been reported that metallocene-alumoxane catalysts produoe polymers of generally lower molecular weight and comonomer incorporation than desired. The application further reports that it would be desirable to support cationic complexes without the use of an alumoxane or alkyl ~ min~lm cocatalys~

Accordingly, there is also a need for an olefin polymerization catalyst that can be used to more effici~ntly and effectively copolymerize ethylene with higher alpha-olefins, e.g. alpha-olefins having 3 to 18 carbon atoms. In practice, the commercial copolymers are made using alpha-olefin monomers having 3 to 8 carbon atoms (i.e., propylene, butene-1, hexene-l, octene-l and 4-methyl-1-pentene) because of the low rate of reactivity and incorporation of the alpha olefins with larger carbon chains because the tr~ifior-~l Ziegler catalysts are not çfficit nt or effective in incorporating the longer chain comonomers into the polymer. There is a need for an olefin polymeri7~tion catalyst which is able to efficiently incorporate a large degree of longer chain olefins into a copolymer chain and give a polymeric - 4 -WO 94/07928 2 1 ~ 6 0 ~ ~ PCr/US93/09377 product which has a narrow molecular weight distribution and is homogeneous with respect to branching. The properties and advantages of homogeneous copolymers are described in US Patent 3,645,992.

Patents and publications which reflect the technology of vinyl addition polymerization, particularly with respect to olefin polymerization, include U.S.Patent Nos.: 4,808,561; 4,935,397; 4,937,301; 4,522,982; 5,026,798; 5,057,475;
5,055,438; 5,064,8025,096,867; European Patent Publication Nos.: 0 129 368, published December 27th, 1984; 0 260 999 published March 23rd, 1988; 0 277 004, published August 3rd, 1988; 0 416 815 published March 13th, 1991; 0 420 431 published April 3rd, 1991; and International Patent publication Nos.: WO
91/04257, published April 4th, 1991; WO 91/14713, published October 3rd, 1991;
and WO 92/00333, published January 9th, 1992.

The present invention provides new and advantageous supported catalyst compositions, new and advantageous supports for catalyst compositions, a processfor preparing these new supports, a process for preparing the supported catalystcompositions, and a process for polymerizing olefins using these new supported catalyst compositions. The new and advantageous supports are prepared by Co.~ g silica with an ~luminox~np~ preferably either methyl~luminoxane or modified methyl~lnminoxane. The new and advantageous supported catalyst compositions combine these supports with a variety of org~nomPt~ catalyst compositions including, for example, constrained geometry catalyst complexes andmetallocene catalysts. Olefins may be advantageously polymPri7Pd using these newsupported homogeneous catalyst compositions, especially ethylene homopolymers and copolymers. Long chain olefins may also be advantageously copolymeriæd -~40,537-F , ,, ~ r r ~2~1~60l 2 with short chain olefins using ~hese new supported homogeneous catalyst compositions Additionally, the new supported homogeneous catalyst compositions are useful in solution polymerization, slurry polymerization and gas-phase polymerization of olefins SUMMARY OF THE INVENTION

The supported homogeneous organometallic catalyst complexes of ~he present invention are a three-component catalyst system comprising:
(a) an organometallic eomplex of ~he formula:

Z' C p*/--\M (I) Q()n l 5 wherein:
M is a metal of Group 4 of the Periodic Table of the Elements, Cp* is a cyclopentadienyl group bound in an ~5 bonding mode to M or such a eyelopentadienyl group substituted with from one to four substituents selected from the group consisting of hydroearbyl, silyl, germyl, halo, hydroearbyloxy, amine, and mixtures ~hereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z' is a divalent moiety other than a cyclopentadienyl group or substituted cyclopentadienyl group, said moiety having up to 20 non-hydrogen atoms and;
X independently each oeeurrenee is an anionic ligand group having up to 50 non-hydrogen atoms and X is not a eyelopentadienyl or substituted eyclopentadienyl group; and n is I or 2 depending on the valence of M;

AMENDED SH~

~0 537-F ; 2~ O12 (b) a compound or complex capable of converting thc organometallic coMplex (a) into a cationic complex of the formula:

C p*--M ~ A- ( I I ) S (X)r~

wherein:
Cp*, Z', M, X, and n are as dclincd with respcct to previous formula I, and 0 A- iS a monovalent, noncoordinating, compatible anion.

(c) a catalyst support in contact with (a) and (b), said catalyst support comprising silica reacted wi~h a methylaluminoxane, a modifled methylaluminoxane, or a mixture thereof.
The supported organometallic catalyst compositions of the present invention: (a) are resistant to the effects of catalyst poisons, (b) they have extended catalyst lifetimes and improved polymerization efrlciencies, particularly with respect to polymerization of long chain olefm monomers, (c) they can be used to provide copolymers, particularly polyolerm copolymers, terpolymers, etc., that have a narrow molecular weight distribution, (d) ~hey provide efficient incorporation of long chain monomers, particularly higher alpha-olefm monomers, into olefinic polymers such that the distribution of long chain monomers in the resultant polymer is homogeneous with respect to both the molecular weight distribution and the distribution of the long chain monomers in the polymer chain, and (e) the novel supported organometallic catalyst AMENDED SH~T

WO 94/07928 2 1 4 6 0 1 2 PCr/US93/09377 compositions are not restricted to any particular polymeri7~tion process, but can be used in gas-phase polymerization, slurry polymerization or solution polymerization of olefins.

DEFINITIONS

All reference to the Periodic Table of the F.l~.ml~.nt.~ herein shall refer to the Periodic Table of the Elements, published and copyrighted by CE~C Press, Inc., 1989. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering Groups.

Group or Groups - Any references to a Group or Groups shall be to the Group or Groups using the IUPAC system for numbering groups of elements.

MAO - all references refer to methylaluminoxane.
MMAO - all references refer to modified methylaluminoxane.

Non-coordinating anion - all references refer to an anion that does not complex or coordinate with the organomet~llic complex of component (a), described below, orwhich is only wealdy coordinated therewith, thus re.m~ining sufficiently labile to be pl~ced by a neutral Lewis base. A non-coortlin~ting, compatible anion specifically refers to a compatible anion which when functioning as a charge balancing anion in the catalyst composition of the invention, does not transfer an anionic substit~lent or fragment thereof to a cationic species of component (a) thereby forming a neutral four coordinate metallocene and a neutral metal by-40,537-F 2146012 -product.

Homogeneous catalyst complex - all references refer to a catalyst which provides a polymerization product that has a narrow molecular weight distribution and, for copolymers, a random dis~ribution of comonomer molecules along the polymer backbone and are homogeneous belween molecules with respect to Lheir comonomer content.

Ziegler catalyst - all references refer to complex generally derived from tilanium halide and a metal hydride or a metal alkyl. These complexes and methods for preparation aré disclosed in U.S. Patents 4,302,565, 4,302,566, 4,303,771, 4,395,359, 4,405,495, 4,481,301 and 4, 562,169. These catalysts usually operate at atmospheric pressure and may be used to polymerize ethylene to linear polyethylene.
DETAILED DESCRIPTlON OF THE INVENTION

The supported organometallic catalyst complexes of the invention are adapted to produce a homogeneous polymer or copolymer. The catalysts generally comprise the reaction product of:

(a) an organometallic complex of.the formula:

Z (I) C p*--M
(X)n wherein:

A~ ENDED S~

~0 537-F
~. 21~6D12 .

M is a metal of Group 4 ol the Pcriodic Table of the Elements, Cp* is a cyclopentadienyl group bound in an ~5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amine, and mixtures thercof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z' is a divalen~ moie(y other than a cyclopentadienyl group or substituted cyclopentadienyl group, said Z' comprising boron, or a member of Group 14 of 10 . the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 20 non-hydrogen atoms ~
and;
X independently each occurrence is an anionic ligand group having up to 50 non-hydrogen atoms and X is not a cyclopentadienyl or substituted cyclopentadienyl group; and n is 1 or 2 depending on the valence of M;
(b) a compound or complex capable of converting the organometallic complex (a) into a cationic complex of the formula:

Z' (II) C p*--M\ + A-(X)r~1 -whereln:
Cp*, Z', M, X, and n are as defined with respect to previous formula I, and A- is a monovalent, noncoordinating, compatible anion.

(c) a catalyst support in contact with (a) and (b), said catalyst support comprising silica reacted with a methylaluminoxane, a modified methylaluminoxane, or a mixture thereof.

A~AE~lD~D SHEE~

40,537-F ~, , ... .
~146012 Suitable organometallic complexes for use herein preferably include constrained geometry complexes, one species of which are also known as bridged monocyclopentadienyl metal catalysts. Examples of such complexes and methods for their preparation are disclosed in U.S. Application Serial No. 07/545,403, filed August 31, 1989, U.S.Application Serial No. 545,403, filed July 3, 1990 (EP-A-416,815); U.S.
Application Serial No. 547,718, filed July 3, 1990 (EP-A-468,651); U.S.
Application Serial No. 702,475, ~lled May 20, 1991 (EP-A-514,828); U.S.
Application Serial No. 876,268, filed May 1, 1992, (EP-A-520,732) and U.S.
Application Serial No. 08/008,003, filed January 21, 1993, as well as U.S.
Patents: 5,055,438, 5,057,475, 5,096,867, 5,064,802 and 5,132,380.

The foregoing catalysts may be further dcscribed as comprising a metal coordination complex, CG, comprising a metal, M, of Group 4 of the Periodic Table of the Elements and a delocalized7~-bonded moiety substituted with a constrain-inducing moiety, said complex having a constrained geometry about the metal atom, and provided further that for such complexes comprising more than one delocalized, substituted 7c-bonded moiety, only one thereof for each metal atom of the complex is a cyclic, delocalized, substituted 7r-bonded moiety.

By the term "constrained geometry" as used herein is meant that the metal atom in the metal coordination complex is forced to greater exposure of the active catalyst site because one or more substituents on the delocalized ~I-bonded moiety forms a portion of a ring structure including the metal atom, wherein the metal is both bonded to an adjacent covalent moiety and held in association with the delocalized -bonded group through an 115 or other 7~-bonding interaction. It is understood that each respective bond between lhe metal atom and the constituent atoms of the 7~-bonded moiety need not be equivalent. That is, ~he metal may be symmetrically or unsymmetrically 7~-bound thereto.

The geometry of the active metal site of the preferred substituted monocyclopentadienyl group containing constrained geometry complexes is further defined as follows. The centroid of the substituted cyclopentadienyl group may be ~MENDE~

~40,537-F
` 214~012 defined as the average of the respective X, Y, and Z coordinates of the a~omic centers forming the cyclopentadienyl ring. The angle, formed at Lhc mctal centerbetween the centroid of the cyclopentadienyl ring and each oLher ligand of the metal complex may be easily calculated by standard techniques of single crystal X-ray diffraction. Each of these anglcs may incrcase or decrcase depending on the molecular structure of the constrained geometry metal complcx. Thosc complcxes wherein one or more of the angles, is less than in a similar, comparativc complex differing only in the fact that ~he constrain-inducing substiLucnt is rcplaccd by hydrogen have constraincd geometry for purposcs of thc prcscnL invcnLion. Thc angle, which is the angle formed beLween the ccntroid of LhC subslitu~cd cyclopentadienyl group, M and the substituent a~tachcd ~o M and the cyclopcntadienyl group is less than in a comparative complex whcrcin Lhe substituent is hydrogen and lacks a bond to the cyclopentadienyl group.
Preferably, monocyclopentadienyl metal coordination complexes used according to the present invention have constrained geometry such that the smallest angle, isless than 115, more preferably less than 110, most preferably less than 105.
Highly preferably, the average value of all bond angles, is also less than in the comparative complex.

Examples of delocalized ~-bonded moieties include Cp* as defined hereinafter . Examples vf constrain inducing moieties include - Z'- or-Z-Y- as defined hereinafter, as well as difunctional hydrocarbyl or silyl groups, mixtures thereof, and mixtures of the foregoing with a neutral two electron donor ligand selected from Lhe group consisting of OR*, SR*, NR*2, or PR*2, wherein R* is as defined hcreinafter.
Preferred metals are the Group 4 metals with titanium being most preferred.

It should be noted that when the constrain- inducing moieLy comprises a neutral two electron donor ligand, the bond between it and M is a coordinate-covalent bond. Also, it should be noted that the complex may exist as a dimer orhigher oligomer. A neutral Lewis base, such as an ether or amine compound, may also be associated with the complex, if desired, however, such is generally not preferred.

AMENDED Si~ T

~537-F 2146012 Preferably still, such metal coordination complexes correspond to the formula III:

.

~0 537-~
~21~6'01'2 R' ~ Z y (III) R ' <~ M~ (X)n ~, R' wherein R' each occurrence is independently selected from the group consisting of hydrocarbyl, silyl, germyl, h~lo, hydrocarbyloxy, amine, and mi:cturcs thereof, said substituent having up to 20 non-hydrogen atoms, or optionally, twohydrocarbyl substituents together c~use Cp$ to have a fused ring structure ~ divalen~
derivative thereof;
X each occurrence independently is an anionic ligand group selected from ~he group consisting of hydride, halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide, siloxy, and combinations thereof having up to 20 non-hydrogen atoms.
Y is a divalent ligand group selected from nitrogen, phosphorus, oxygen and sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur;

M is a Group 4 metal, especially tit nium;
ZisSiR 2- CR*2, SiR 2SiR*2, CR*2CR 2 (~R*=CR*, CR*2SiR*2 GeR*2, or BR* wherein:
R* each occurrence is independently selecLed from ~he group consis~ing of hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non- hydrogen atoms, and mixtures thereof, n is 1 or 2.

~lost highly preferred metal coordination complexes correspond to the formula (IV):

AA7~NDED S~ET

.
40,537-F ' ~ 6 ~ 2 R' (ER 2)m~
/--/ N--R ' ( IV) R ~<0---M/
(X)n 1, R' wherein:
M is titanium bound in a ~5 bonding mode Lo the cyclopcnt~dienyl g,roup;
R' at each occurrence is independently selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amine, and mixtures thereof, said substituent having up to 10 carbon or silicon atoms, or two R' groups within thecyclopentadienyl structure form a fused ring;
E is silicon or carbon;
X independently each occurrence is selected from hydride, halo, alkyl, aryl, aralkyl, aryloxy and alkoxy of up to 10 carbons;
m is 1 or 2; and n is 1 or 2.

Examples of the above most preferred metal coordination complexes include complexes wherein the R' on the amido group is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, (including all isomers of said propyl, . butyl, perityl, hexyl groups), norbornyl, benzyl, phenyl, etc.; the cyclopentadienyl group is cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, etc.; R' on ~he foregoing cyclopentadienyl g~oups each occurrence is a hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, etc.; and X is a chloro, bromo, iodo, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, etc.

Specific highly preferred compounds include: (tert-butylamido)(tetra-methyl-~5- cyclopentadienyl)-1,2- ethanediyltitanium dimethyl, (tert-butylamido)(tetramethyl-~5-cyclopentadienyl)-l~2-ethanediyltitanium dibenzyl, (tert-butylamido)(tetramethyl-1l5- cyclopentadienyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-1l5- cyclopentadienyl)dimethylsilaneti~nium dibenzyl, (methylamido)(tetramethyl-tl5-cyclopentadienyl)dimethylsilane~itanium dimethyl, AMENDED ~ T

40,537-F 2 1 ~ ~ O ~ 2 (methylamido)(tetramethyl-~5-cyclopentadienyl)dimethylsilanetitanium dibenzyl, (phenyl~mido)(tetramethyl-~5-cyclopentadienyl)dimethylsilanetitanium dimethyl, (phenylamido)(tetramethyl-~5-cyclopentadienyl)dimethylsilanetitanium dibenzyl, (benzylamido) (tetramethyl-~ 5- cyclopentadienyl)dimethylsilanetitanium dimethyl, S (benzylamido)(tetramethyl-rl5-cyclopentadienyl)dimethylsilanetitanium dibenzyl, (tert-butylamido)(~5- cyclopentadienyl)-l~2-ethancdiyllitanium dimelhyl, (tert-butylamido)(~5- cyclopentadienyl)- 1,2- ethanediyltitanium diben%yl, (tert-butylamido)(~5- cyclopenta(3ienyl)dimethylsil,mctitanium dimcthyl, (tcrt-butylamido)(~5-cyclopcnladicnyl)(iimcLhylsilanctitaniunl dibenzyl, (mcLtlylanlido)(rl5 cyclopentadienyl)dimcthylsilanetitanium dimcthyl, (t-butylanlido)(~5-cyclopenta dienyl)dimethylsilanetitanium dibenzyl, (t- butylamido)indenyldimethylsilane-titanium dimethyl, (t- bu~ylamido)indenyldimethylsilanetitanium diben%yl, (benzylamido)indenyldimethylsilanetitanium dibenzyl; and the corresponding zirconium or hafnium coordination complexes.
The complexes may be prepared by contacting a metal reactant of the formula: MXnX'2 wherein M, X, and n are as previously defined, and ~' is a suitable leaving group, especially halo, with a double Group I metal derivative or double Grignard derivative of a compound which is a combination of the 20 delocalized ~-bonding group having the constrain inducing moiety, especially C-Cp-Z'-M', wherein M is the Group I metal or Grignard, attached thereto. The reaction is conducted in a suitable solvent and the salt or other byproduct is separated. Suitable solvents for use in preparing the metal complexes are aliphatic or aromatic liquids such as cyclohexane, methylcyclohexane, pentane, hexane, heptane, tetrahydrofuran, diethyl ether, benzene, toluene, xylene, ethylbenzene,etc., or mixtures thereof. This technique is described in EP 0416815.

Ionic, active catalyst species, which are formed by combining (a) as defined above and (b) as defned herein, preferably corresponding to the formula (II) .

AMENDED SHEET

0,537-F
21~6012 Cp* - M + A- (II) (X)n-l .

whcrcin:
Cp*, Z', M, X, and n are as ~I~ined witll r~spect lo previous formula I, and A- is a monovalent, noncoordinaling, compatible anion 0 Preferred ionic catalysts correspond to the formula (V):
R' R-- ~ - / + A ( V ) ~\ (X)n-1 R ' wherein:
R', Z, Y, M, X, and n are as defmed with respect to previous formula (lll), and A- is a monovalent, noncoordinating, compatiblc anion.
Most preferred ionic catalysts correspond to the formula Vl:
,(ER '2)m~
~ N--R ' R~--M~ A (Vl ) R' (X)n-1 whcrcin:
R', E, M, N, m and n are as defined with respect to prcvious formula (IV), and A- is a monovalent, noncoordinating, compatible anion.

One method of making th~sc ionic catalysts involvcs combining:

A)YtE~(D~D SH~T

~,537-F r r 2 ~ 4 6 0 f 2 al) Lhe previously disclosed meLal coordination coMplex containing at least one substituent which will combine with the cation of a second component, and b1) at least one second component which is a salt of a Bronsted acid and a noncoordinating, compatible anion.

More particularly the noncoordinating, compatible anion of the Bronsted acid salt May comprise a single, non- nucleophilic, coordination complex comprising a charge-bearing metal or nonmetal core. Preferred anions comprise aluminum, silicon, boron, or phosphorus.

Preferred metal complexes for Lhe foregoing reacLion are Lhose containing at least one hydride, hydrocarbyl or substituted hydrocarbyl group. The reaction is conducted in an inert liquid such as tetrahydroturan, Cs 10 alkanes, or toluene.
Compounds useful as a second component (b) in the foregoing preparation of the ionic catalysts in step bl) will comprise a cation, which is a Bronsted acid capable of donating a proton, and the anion A-. Preferred anions are those containing a single coordination complex comprising a negative charge bearing core which anion is capable of stabilizing the active catalyst species (the metal cation) which is formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers, nitriles and the like. Compounds containing anions which comprise coordination complexes containing a single core atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion,are available commercially. In light of this, sal~s containing anions comprising a coordination complex containing a single boron atom are preferred.

AM~NDE~ SHEET

2 i 1 6 0 1 2 Second components (b) comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general fomlula (VII) [L-H]+ ~BQ4]- (VII) wherein:

L is a neutral Lewis base;
[L-H]+ is a BronsLed acid;
B is boron in a valence sLate of 3; and Q is a Cl 20 fluorinated hydrocarbyl group. Most preferably, Q is each occurrence a perfluorinated aryl group, especially, tetrakis-pentaQuorophenylborate.

AMENDED SHEET

W O 94/07928 214 G O 12 PC~r/US93/09377 Illustrative, but not limiting, examples of boron compounds which may be used as a second component in the preparation of the improved catalysts of this invention are trialkyl ammonium salts or triaryl ammonium salts such as:
trimethylammonium tetraphenylborate, N,N-dimethyl~nilinillm tetraphenylborate, S trimethylammonium tetrakisperfluorophenylborate, triethylammonium tetr~kicperfluorophenylborate, tripropylammonium tetrakisperfluorophenylborate, tri(n-butyl)ammonium tetrakisperfluorophenylborate, tri(t-butyl)ammonium tetra~kisperfluorophenylborate, N,N-dimethyl~nilinium tetrakisperfluorophenylborate, N,N-diethylanilinium tetrakisperfluorophenylborate, N,N-(2,4,6-pentamethyl)anilinium tetrakisperfluorophenylborate, trimethylammonium tetrakis- (2,3,4,6-tetrafluorophenylborate, N,N-dimethyl-~nilinillm tetrakis-(2,3,4,6-tetrafluorophenylborate, N,N-(2,4,6- penta-methyl)anilinium tetrakis-(2,3,4,6- tetrafluorophenylborate, and the like; dialkyl ammonium salts such as di-(i-propyl)ammonium tetrakis-pentafluorophenylborate, dicyclohexylammonium tetrakis-pentafluorophenylborate and the like; and triaryl substituted phosphonium salts such as triphenylphosphonium tetrakis-pent~fluorophenylborate, tri(o- tolyl)phosphonium tetrakis-pentafluorophenylborate, tri(2,6- dimethylphenyl)phosphonium tetrakis-pentafluorophenylborate, and the like.
Another technique for preparing the ionic complexes involves combining:
a2) the previously disclosed metal coordination complex (first component); and b2) at least one second component which is a salt of a calLenium and the previously disclosed noncoordin~ting~ compatible anion, A-.

Another technique for plt;p~hlg the ionic complexes involves combining:
a3) a reduced metal deflvaliv~ of the desired metal coor lin~tion complex wherein the metal is in an oxidation state one less than that of the metal in the finichPd complex; and b3) at least one second component which is a salt of a cationic oxidizing agent and a noncoordin~ting, compatible anion.

The second component useful in this preparation of the ionic catalyst used ~40537-F ` ~146012 in this invention may bc rcprcsented by thc following gcneral formula VllI:

(Ox~ ) (A ~)~ ( VIII ) whercin:
OxC+ is a calion;c oxidi%ing agent having a charge of +e; and A ~ is as previously dcfined.

Preferred cationic oxidi%ing agenls include: ferrocenium, bisindcnyl Fe(III), cationic derivatives of substituted l`errocenium, Ag+, Pd+2, pt+27 Hg+2, Hg2+2, Au+, or Cu+. Prefcrrcd cmbodimcnts of A ~ arc those anions prcviously defined, especially, tetrakis(perfluorophenyl)borate.

A still further technique for preparing the ionic complexes involves combining:
a4) a reduced metal derivativc of thc desired metal coordination complex wherein the metal is in an oxidation state one less than that of the metal in the finished complex; and b4) at least one second component which is a neutral oxidizing agent in combination with a Lewis acid mitigating agent Suitable oxidizing agents are quinone compounds, especially bisquinones. Suitable Lewis acid mitigating agents include tris(perfluorophenyl)bor~ne.

A final technique for preparing the ionic complexes is an abstraction technique involving combining:
aS) the previously disclosed metal coordination complex (first component); and bs) a Lewis acid having sufficient Lewis acidity to cause abstraclion of an anionic ligand of the metal coordination complex thereby forming a cationic derivative thereof.

Preferred metal coordination complexes for the foregoing abstraction reaction are those containing at least one hydride, hydrocarbyl or substituted hydrocarbyl group able to be abstracted by the Lewis acid. A preferred compound for abstracting the Lewis acid AMEND~D SHEE~

~40 537-F
2l~Gal2 is tris(pernuorophenyl)boranc.

Ionic complexes resulting rrom the l~ter abstraction technique have a limiting charge separated structurc corrcspondino to the formula IX:

CG'+(XA' ) (IX) -wherein:
CG' is the dcrivative formcd by ahstraction of an X group from thc metal complex, which is as prcviously dciined in it broadcst, preferred and most prefcrred embodiMenls;
X is the anionic ligand abstractcd IroM thc mctal coordination complcx;
and A' iS the remnant of the Lewis acid. Preferably X is Cl-CIo hydrocarbyl, most preferably methyl.

The preceding formula is referred to as the limiting, charge separated structure. However, it is to be understood that, particularly in solid form, thecatalyst may not be fully charge sep~rated. That is, the X group may retain a par~ial covalent bond to the metal atom, M. Thus, the catalysts may be alternately depicted as possessing the formula:

CG" - X~A

wherein CG" is the partially charge separated CG group.

Other catalysts ,which arc useiul as the catalyst compositions of this invention, especially compounds containing other Group 4 metals, will, of course, be apparent to those skilled in the art.
Component (c) of the invention is conveniently made by reacting SiO2 and an aluminoxane. As will be apparent to those skilled in the art based upon the teachings herein, generally the higher surface area of the SiO2 of component (c) the AME~DED SHEET

wo 94/07928 2 1 4 6 0 1 2 PCr/US93/09377 better. Therefore, in general, the SiO2 of component (c) is preferably a porous, fine particulate having a large surface area. Nevertheless, the particle siæ of the SiO2 of component (c) will depend on whether the homogeneous three-component catalyst is to be used in a gas-phase polymerization process, a slurry polymerization process, or a solution polymerization process.

Preferably, for use in an olefin polymerization process, the SiO2 of component (c) has a porosity of from 0.2 to 1.5 cubic centimeter per gram (cc/g), more preferably from 0.3 to 1.2 cc/g, and most preferably from 0.5 to 1.0 cc/g, each being a measure of the mean pore volume as determined by the BET technique using nitrogen as a probe molecule.

Preferably, for use in a gas-phase olefin polymeri7~tion process, the SiO2 of component (c) has an mean particle diameter from about 20 microns to 200 microns, more preferably from 30 microns to 150 microns and most preferably from 50 microns to 100 microns, each as measured by sieve analysis.

Preferably, for use in a slurry olefin polymerization process, the SiO2 of component (c) has an mean particle diameter from about 1 microns to 150 microns,more preferably from 5 microns to 100 microns and most preferably from 20 microns to 80 microns, each as measured by sieve analysis.

Preferably, for use in a solution olefin polymerization process, the SiO2 of component (c) has an mean particle diameter from 1 microns to 40 microns, more preferably from 2 microns to 30 microns and most preferably from 3 microns to 20 microns, each as measured by sieve analysis.

t ~ ir ~ .f~

40,537-F , ......... ..
~14G012-The silica of component (c) is preferably dehydroxylated prior to reaction with aluminoxane. Dehydroxylation may be accomplished by any suitable means known in the art. A preferred means for the dehydroxylation reaction is heating of a silica powder in a fluidized bed reactor, under conditions well known to thoseskilled in the art. Most preferably, conditions are chosen such that the silica is substantially dehydroxylated prior to reacLion with aluminoxane but, it should be recognized that the silica need not be completely dehydroxylated.

Suitable commercially available silica for use in component (c) of the invention include precipitated silicas, available from the Davison Division of W.
R. Grace & Company in Connecticut.

The aluminoxane of component (c) is of the formula (R4X(CH3)yAlO)n, wherein R4 is a linear or branched or C3 to Clo hydrocarbyl, x is from 0 to 1, y is great-er than 0, and n is an integer from 3 to 25, inclusive. The preferred aluminoxane components, referred to as modified methylaluminoxanes, are those wherein R4 is a linear or branched C3 to Cg hydrocarbyl, x is from 0.15 to 0.50, y is from 0 85 to 0.5 and n is an integer between 4 and 20, inclusive; still more preferably R4 is isobutyl, tertiary butyl or n-octyl, x is from 0.2 to 0.4, y is from 0.8 to 0.6 and n is an integer between 4 and 15, inclusive. Mixtures of the above aluminoxanes may also be employed in the practice of the invention.

AMENDED SHEEt 40,537-F 2 14 6 01~

Component (c) may be readily made by the reaction of SiO2 and aluminoxane in an inert solvent, under an inert atrnosphere, preferably argon ornitrogen, and under anhydrous conditions. Such reaction conditions are well known. Suitable inert solvents include alipha~ic or aromatic organic solvents.

Particularly preferred aluminoxanes are so-called modified aluminoxanes, preferably modified meLhylaluminoxanes (MMAO), that are completely soluble in alkane solvents, for example heptane, and include very liLtlC, if any, trialkylaluminum. A technique for preparing such modified aluminoxanes is disclosed in U.S. Patent No. 5,041,584. Aluminoxanes useful in preparing component (c) of invention may also be made as disclosed in U.S. Patent Nos.
5,542,199; 4,544,762;, 5,015,749; and 5,041,585.

Use of aliphatic solvents is generally preferred in the preparation of component (c) of the invention, since these solvents are generally readily removed from the final polymerization product by devolatilization and they are thought to present minimal, if any, health risks in either the manufacture of the polyolefin product, in particular ethylene homopolymers and copolymers, or in the polyolefin product itself. Although, aromatic solvents, such as toluene, benzene, and the like, can also be used in the preparation of component (c) of the invention, they are not generally preferred.

A wide range of liquid aliphatic hydrocarbons can be used as solvents, including mixtures of such hydrocarbons. This known class of compounds includes, for example, pentane, hexane, heptane, isopentane, cyclohexane, p~ENDE~3 S

.

WO 94/07928 2 1 ~ ~ ~ 1 2 PCr/US93/09377 methylcyclohexane, isooctane, and the like, and mixtures of thereof, such as commercial blends Of C8 to Clo alkanes sold under the tradename Isopar E by Exxon (~hPmic~l Co. Most preferably, the solvent for making component (c) of theinvention is n-heptane.
While the order of addition of the SiO2 and ~hlminoxane and solvent is not thought to be critical in preparing component (c), it is generally preferred to add the aluminoxane to a slurry of SiO2 in the inert solvent. It is also preferred that the SiO2 and aluminoxane mixture be stirred throughout the reaction in order to expedite the reaction process by providing and m~int~ining an intim~t~ contact between the reactants.

The reaction between SiO2 and aluminoxane in making component (c) of the invention may be performed a temperatures between about -20C and about 120C, preferably between about 0C and about 100C, more preferably between about 20C and about 80C, and most preferably between about 40 and about 70C, all preferably at about atmospheric pressure. The time of the reaction between SiO2 and ~lllminoxane may be from about 15 min~ltes (min) to about 24 hours, preferably from about 30 min to about 12 hours, more preferably from about 1 hour to about 8 hours, and most preferably from about 2 hours to about 4hours, in accordance with the conditions of temperature and ples~u.e set forth above.

The time and temperature required for the completion of the reaction between SiO2 and aluminoxane may readily be determined for any particular batch of starting materials and solvents by monitoring evolution of gaseous by-products, .
. .

W O 94/07928 ~ ~ 4 6 ~ 1 2 PC~r/US93/09377 the reaction being complete when no further by-product evolution occurs.

While it is most preferred that the SiO2 of component (c) is reacted to saturation with an aluminoxane, less than full saturation of the SiO2 is operable in the product and process of the invention; however, the resultant supported homogeneous catalyst is expected to operate at less than optimal efficiencies, and thus is not desired.

The supported homogeneous organometallic catalyst of the present invention is readily prepared by combining and reacting component (a), component(b) and component (c), in any order, after which the supported organometallic catalyst thereby obtained is introduced into a polymerization reactor vessel. Thus, component (a) may first be reacted with component (b), and component (c) is subsequently added to the reaction product of components (a) and (b).
Altern~tively, component (a) may be added to a mixture of components (b) and (c), and the reslllt~nt product of the reaction between components is added to the polymerization reactor. Preferably, component (a) is first reacted with component (c), and the reaction product is then mixed with the activator component (b), and the result~nt activated supported catalyst is added to the polymP.ri7~tion reactor. In general, the catalyst composition of the invention can be prepared by combining components (a), (b) and (c) in a suitable solvent or rlihltP.nt typically a mixture of C8 to Clo saturated hydrocarbons (e.g., Isopar E made by Exxon) at a temperaturewithin the range of from -100 C to 300 C, preferably from 0 C to 200 C, and more preferably from 25 C to 150 C. After the addition of all three components to 25 the reaction medium, the re.s-llting activated catalyst may be isolated as a solid from the reaction mixture, such as by filtration. The isolated, activated supported 2~0~2 WO 94/07928 PCr/US93/09377 catalyst may then be added to the polymerization reactor, if so desired, especially for gas phase polymerization processes.

It has been found that the composition of component (a) and component (c) is surprisingly stable. For example, such a composition has been found to be ec.cçnti~lly fully activatable by component (b) up to about one month after the mixing of components (a) and (c). Such a stability represents another advantage of the present invention, in that a batch mixture of components (a) and component (c) can be initially made, and shipped if necess~ry, and later be made into the active catalyst of the invention. As such, the processes using the supported catalyst complexes of the invention are expected to be more reproducible from batch to batch than was heretofore attainable.

In addition, the mixture of the activated catalyst cont~ining all three components, or the solid, supported, activated catalyst isolated from the reaction mixture after all three components have been added, is also surprisingly stable.

In the practice of the invention, the mole ratio of component (b) to component (a) is from 0.01:1 to 100:1, preferably from 0.1:1 to 20:1, and more preferably from 0.5:1 to 10:1. The mole ratio of Al in component (c) to metal, M, in component (a) is from 0.1:1 to 10,000:1, preferably from about 1:1 to 500:1, and more preferably from 3:1 to about 100:1.

Hydrogen or other chain transfer agents (i.e., telogens) can also be employed in the polymerization of olefins in the practice of the invention to control the chain length of polymers. The class of materials which can be used to control 2146~12 W O 94/07928 PC~r/US93/09377 chain length of olefinic polymers especially ethylene homopolymers and copolymers during polymerization and methods of using such m~te.ri~ for that purpose are known in the art. Generally, the molar ratio of hydrogen to olefin monomer(s) is from 0 to 1; preferably from 0 to 0.1; and, most preferably from 0 to about 0.05.

The polymerization reaction especially the polymerization of ethylene homopolymers and copolymers in the practice of the present invention in a solution polymerization process may be conducted under temperatures and pressures in such combinations as to provide acceptable polymerization efficiencies and as well as the desired molecular weight interpolymers. The useful ranges for these processes are readily detPrmine.d by those skilled in the art.

The solution polymerization especially the polymerization of ethylene homopolymers and copolymers may be either a "high pressure" or "low pressure"
process. Suitable reactor pressures for a solution polymP.ri7~tion for the above temperature ranges are from about atmospheric pressure to 1000 psig (6900 kPa), preferably from 15 psig to 700 psig (100 kPa to 4800 kPa), and most preferably from 200 psig to 600 psig.

As would be readily recognized by those skilled in the art, the useful polymPri7~tion reaction temperatures and pressures for slurry polymPri7~tion and gas-phase polympri7~tion can be readily ~letprminp~d~ and are generally those that are known.

Suitable solvents or diluents in the polymerization reaction include those .

WO 94/07928 2 1 ~ ~ O 1 2 PCr/US93/09377 compounds known to be useful as solvents or diluents in the polymerization of olefins and diolefins. Suitable solvents or diluents include, but are not meant to be limited to, straight and branched chain hydrocarbons, preferably Cl to Clo hydrocarbons, such as isobutane, butane, pentane, isopentane, hexane, heptane, octane, isooctane, nonane, and the like; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methyl cyclohexane, methylcycloheptane, and the like.

Suitable solvents or diluents also include liquid olefins which may act as monomers or comonomers in the polymerization reaction, such as ethylene, propylene, cyclopentene, l-hexene, 3-methyl-1-pentene, ~methyl-l-pentene, 1-octene, l-decene, styrene, and the like.

The polymerization reaction may be performed by any of the conventional polymPri7~tion means which had been used for Ziegler Natta catalyæd reactions.
These include single phase systems wherein the single phase is primarily the principal monomer or an inert diluent. Alternatively, a two-phase polymerizationsystem may be employed where the liquid phase is primarily the principal monomeror an inert diluent. The catalyst compositions of the present invention are particularly suitable for gas-phase or slurry polymerization reaction systems.
In a preferred embodiment, the supported catalyst composition of the invention is used either to homopolymeriæ ethylene or to copolymeriæ ethylene (the most preferred principal monomer) with -olefin comonomers having from 3 to 20 carbon atoms, preferably from 3 to 18 carbon atoms, more preferably from 3 to2~ 12 carbon atoms, and most preferably from 3 to 10 carbon atoms, including styrene, thereby yielding a copolymer. Copolymers of propylene with either ~ ~601~
WO 94/07928 . PCr/US93/09377 ethylene, with either as principal monomer or on an equimolar basis, or copolymers with propylene as principal monomer and C4 to C20, preferably C4 to Clg, more preferably C4 to C12 and most preferably C4 to C1o, alpha-olefin comonomers are also preferred. As would be readily apparent to those skilled in the art, polyolefin copolymers comprising more than two chemically distinct monomeric units (e.g., terpolymers, etc.) may also be conveniently made in the practice of the invention.
It is therefore to be understood that "copolymer", as used herein, is meant to include any polymer comprised of two or more chemically distinct monomeric units.

Preferred monomers include the C2-C 10 -olefins especially ethylene, 1 -propene, isobutylene, l-butene, 1 -hexene, 4-methyl- l-pentene, and l-octene. Other preferred monomers include styrene, halo- or alkyl substituted styrenes, tetrafluoroethylene, vinylbenzocyclobutene, 1,4-he~ iPI~P-, and naphthenics (e.g., cyclopentene, cyclohexene and cyclooctene).

The molecular weight of the ethylene or ethylene/-olefm subst~nti~lly lirlear olefin polymers in the present invention is conveniently represented by I2, as described in ASTM D-1238. Throughout this disclosure, "melt index" or "I2" is measured in accordance with ASTM D-1238 (190C/2.16 kg); "Ilo" is measured in accordance with ASTM D-1238 (190C110 kg). For linear polyolefins, especially linear polyethylene, it is well known that as Mw/Mn increases, Ilo/I2 also increases. With the ethylene or ethylene/-olefin ~ubst~nti:~lly linear olefin polymers of this invention, the Ilo/I2 may be increased without increasing Mw/Mn. The melt index for the ethylene or ethylene/-olefin cubst~nti~lly linear olefin polymers used herein is generally from 0.01 grams/10 min~ltes (g/10 min) to 1000 g/10 min, preferably from 0.01 g/10 min to 100 g/10 min, and especially from 0.01 g/10 minto 10g/lOmin.

30 The copolymers have a Ilo/12 melt flow ratio of from 6 to 18, and preferably from 6 to 14.

W O 94/07928 PC~r/US93/09377 2 ~

The density of the ethylene or ethylene/-olefin subst~nti~lly linear olefin polymers in the present invention is measured in accordance with ASTM D-792 and is generally from 0.85 g/cm3 to about 0.96 g/cm3, preferably from 0.865 g/cm3 to0.96 g/cm3. The density of the copolymer, at a given melt index level for the copolymer, is primarily regulated by the amount of the comonomer which is copolymeri7Pd with the ethylene. In the absence of the comonomer, the ethylene would homopolymeri_e with the catalyst of the present invention to provide homopolymers having a density of about >0.95. Thus, the addition of progressively larger amounts of the comonomers to the copolymers results in a progressive lowering of the density of the copolymer. The amount of each of the various -olefin comonomers needed to achieve the same result will vary from monomer to monomer, under the same reaction conditions. Thus, to achieve the same results, in the copolymers, in terms of a given density, at a given melt index level, larger molar amounts of the different comonomers would be needed in the order of C3>C4>Cs>C6>C7>Cg.

Preferably, the polymeri7ation temperature is from about 0C to about 110C, using constrained geometry catalyst technology. If a narrow molecular weight distribution polymer (MW/Mn of from 1.5 to 2.5) having a higher Ilo/I2 ratio (e.g. Ilo/I2 of 7 or more, preferably at least 8, especially at least 9) is desired, the ethylene partial pressure in the reactor is reduced. Generally, manipulation of Ilo/I2 while holding MWlMn relatively low for producing the novel polymers descnhed herein is a function of reactor temperature and/or ethylene and comonomer concentration.

The term "subst~nti~lly linear" polymers means that the polymer backbone is substitllted with 0.01 Iong chain branches/1000 carbons to 3 long chain branches/1000 carbons, more preferably from about 0.01 long chain branches/1000 carbons to 1 long chain branches/1000 carbons, and especially from 0.05 long chain branches/1000 carbons to 1 long chain branches/1000 carbons.

The term "linear olefin polymers" means that the olefin polymer has no long chain branching, as for example the traditional linear low density polyethylene 2 ~ I 2 W O 94/07928 PC~r/US93/09377 polymers (including the sub-set of polymers known as very low density polyethylene (VLDPE) or alternatively known as ultra low density polyethylene (ULDPA)) or linear high density polyethylene polymers which are heterogeneously branched polymers made using Ziegler polyme;ization processes (e.g., USP
4,076,698 or USP 3,645,992, which are incorporated herein by reference). The term "linear olefin polymers" does not refer to high pressure branched polyethylene, ethylene/vinyl acetate copolymers, or ethylene/vinyl alcohol copolymers which are known to those skilled in the art to have numerous long chain branches.
Long chain branching is defined herein as a chain length of at least 6 carbons found in ethylene homopolymers, above which the length cannot be distinguished using 13C nuclear magnetic resonance spectroscopy. The long chain branch can be as long as about the same length as the length of the polymer back-bone.

Long chain branching is determined by using 13C nuclear magnetic resonance (NMR) spectroscopy and is quantified using the method of Randall (~ Macromnl.Chem. Phvs., C29 (2&3), p. 285-297).
"Melt tension" is measured by a specially designed pulley transducer in conjunction with the melt indexer. Melt tension is the load that the extrudate or f11~mçnt exerts while passing over the pulley at the standard speed of 30 rpm. The melt tension measul~l"ent is similar to the "Melt Tension Tester" made by Toyoseiki and is described by John Dealy in "Rheometers for Molten Plastics", published by Van Nostrand Reinhold Co. (1982) on page 250-2~1.

The SCBDI (Short Chain Branch Distribution Index) or CDBI
(Composition Distribution Branch Index) is defined as the weight percent of the polymer molecules having a comonomer content within 50 percent of the median total molar comonomer conten~ The CDBI of a polymer is readily calculated from data obtained from techniques known in the art, such as, for example, temperature rising elution fractionation (abbreviated herein as "TREF") as described, for example, in Wild et al, Journal of Polymer Science. ~QI~ Phvs. Ed., Vol. 20, p.

WO 94/07928 ~ 2 PCr/US93/09377 441 (1982), or in U.S. Patent 4,798,081. The SCBDI or CDBI for the new polymers of the present invention is preferably greater than about 30 percent, especially greater than about 50 percent. These resins are characteriæd in that they have a single melting point as deterrnined using Differential Sc~nning Calorimetry (DSC).

A unique characteristic of the presently claimed polymers is a highly unexpected flow property where the I10ll2 value is essenti~lly independent of polydispersity index (i.e. MWlMn). This is contrasted with conventional polyethylene resins having rheological properties such that as the polydispersity inde~ increases, the I lo/I2 value also increases.

The whole interpolymer product samples and the individual interpolymer samples are analyzed by gel permeation chromatography (GPC) on a Waters 150C
high temperature chromatographic unit equipped with three mixed porosity columns(Polymer Laboratories 103, 104, 105, and 106), operating at a system temperatureof 140C. The solvent is 1,2,4-trichlorobenzene, from which 0.3 percent by weight solutions of the samples are prepared for injection. The aow rate is 1.0 milliliterctminute and the injection siæ is 200 microliters.
The molecular weight determination is deduced by using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) in conjunction with their elution volumes. The equivalent polyethylene molecular weights are ~etermin~ci by using appropriate Mark-Houwink coefficients for polyethylene and polystyrene (as described by Williams and Word in Journal of Polymer Science~ Polymer Letters. Vol. 6, (621) 1968, to derive the following equ~tion-Mpolyethylene = a * (Mpolystyrene)b-In this equation, a = 0.4316 and b = 1Ø Weight average molecular weight, Mw, is calculated in the usual manner according to the following formula: Mw = R wi*Mi, where Wi and Mi are the weight fraction and molecular weight, respectively, of the ith fraction eluting from the GPC column.

~1~6012 W O 94/07928 PC~r/US93/09377 Processing Index Determination The rheological processing index (PI) is measured by a gas extrusion rheometer (GER). The GER is described by M. Shida, R.N. Shroff and L.V.
Cancio in Polym. Eng. Sci., Vol. 17, no. 11, p. 770 (1977), and in "Rheometers for Molten Plastics" by John Dealy, published by Van Nostrand Reinhold Co.
(1982) on page 97-99. The processing index is measured at a temperature of 190C, at nitrogen pressure of 2500 psig using 0.0296 inch diameter, 20~ D die having an entrance angle of 180. The GER processing index is calculated in millipoise units from the following equation:
PI = 2.15 X 106 dynes/cm2/(1000 X shear rate), where: 2.15 X 106 dynes/cm2 is the shear stress at 2500 psi, and the shear rate is the shear rate at the wall as represented by the following equation:
32 Q~/ (60 sec/min)(0.745)(Diameter X 2.54 cm/in)3, where:
Q' is the extrusion rate (gms/min), 0.745 is the melt density of polyethylene (gm/cm3), and Diameter is the orifioe diameter of the capillary (inches).
The PI is the apparent viscosity of a material measured at apparent shear stress of 2.15 x 106 dyne/cm2 .

For the sllbst~nti~lly linear olefin polymers disclosed herein, the PI is less than or equal to 70 percent of that of a comparative linear olefin polymer at about the same I2 and MwlMn.
An app~nl shear stress vs. apparent shear rate plot is used to identify the melt fracture phe~o,nen~ According to Ramamurthy in 1Q~1 Qf Rheolo~ .
30(2), 337-357, 1986, above a certain critical flow rate, the observed extludateirreg~ ritiPs may be broadly cl~c~ifi~d into two main types: surface melt fracture and gross melt fracture.

Surface melt fracture occurs under appar~"tly steady flow conditions and ranges in detail from loss of specular gloss to the more severe form of ".sh~rk~kin".
In this disclosure, the onset of surface melt fracture is characteriæd at the beginning W 0 94/07928 ~ L ~ 2 PC~r/US93/09377 of losing extrudate gloss at which the surface roughnçss of extrudate can only be detected by 40X m~gnific~tion. The critical shear rate at onset of surface melt fracture for the subst~nti~lly linear olefin polymers is at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear olefin polymer having about the same I2 and MWlMn.

Gross melt fracture occurs at unsteady flow conditions and ranges in detail from regular (~ltern~ting rough and smooth, helical, etc.) to random distortions.
For commercial acceptability, (e.g., in blown film products), surface defects should be minim~l, if not absent. The critical shear rate at onset of surface melt fracture (OSMF) and onset of gross melt fracture (OGMF) will be used herein based on the changes of surface roughness and configurations of the extrudates extruded by a GER.

The polyolefins e~peci~lly ethylene homopolymers and copolymers of the invention may be used to prepare fabricated articles using conventional polyolefin processing techniques. Useful fabricated articles include those such as films (e.g., cast, blown and extrusion coated), fibers (e.g., staple fibers, spunbond fibers or melt blown fibers) and gel spun fibers, both woven and non-woven fabrics (e.g., spunlaced fabrics), and articles made from blends of such fibers, as well as molded articles made, for ex~mple, by conventional injection molding, blow molding and rotomolding processes.

In order that persons skilled in the art may better unclerst~nd the practice of the present invention, the following examples are provided by way of illustration, and not by way of limitation. Additional information which may be useful in state-of-the-art praçti~e may be found in each of the references and patents cited herein.

~0,537-F
~146Q12 Example I

A. Preparalion of (Tert-hutylamido)dimethyl(tetramethyl-nS-cvclo-~entadienyl)silanetitanium dimethyl Complex.
In a drybox, 4.0 mL of 2.0 M isopropylmagnèsium chloride in diethyl e~her was syringed into a 100 mL flask. Thc ethcr was rcmoved undcr rcduccd pressure to leave a colorless oil. 20 mL of a 4:1 (by volume ) toluene:tetrahydrofuran (THF) mixture was added followed by 0.97 g of (Lert-butylamino)dimethyl(tetramethyl-cyclopentadienyl)silane. The solution was heated Lo reQux. AfLer 8-10 hours, a white precipitate began to form. Aher refluxing ror a total of 27 hours, the solution was cooled and the volatile materials were removed under reduced pressure. The white solid residue was slurried in pentane and f~ltered to leave a white powder(1.23 g, 62% yield) of [Me4CsSiMe2N-t-Bu]Mg2C12(THF)2 (where Me is methyl, t-Bu is tertiary butyl and THF is tetrahydrofuran).

In the drybox, 0.10 g of TiC13(THF)3 was suspended in 40 mL of THF.
0.138 g of solid [Me4CsSiMe2N-t-Bu]Mg2C12(THF)2 was added, rcsulting in a color change from pale blue to deep purple, signifying Lhe formation of the complex (tert- butylamido)dimethyl(tetramethyl-n5cyclo-pcntadienyl)silaneLitanium chloride.
After stirring for 5 minutes, 0.17 mL of a 1.56 M solution of methylene chloride in tetrahydrofuran was added. The color changed to bright yellow. After several minutes the THF was removed under reduced pressure. The product was recovered by extraction in pentane. The yield was 70 percent. The product's identity was confirmed as (tert-butylamido)dimethyl-(tetramethyl- nS-cyclopentadienyl)-silanetitanium dichloride by IH NMR, (C6D6): 1.992 (s), 1.986 (s), 1.414 (s), p~~9~1) s~EFr V~O 94/07928 PC~r/US93/09377 2146~12 0.414 (s).

In an inert atmosphere box, 9.031 g of (tert-butylamido)dimethyl-(tetramethyl- nS-cyclopentadienyl)-silanetit~nium dichloride is charged into a 250 mL flask and dissolved into 100 mL of THF. To the solution is added 35 mL of a 1.4 M methylm~gnesium bromide solution in toluene/THF. The reaction mixture is stirred for 20 min follwed by removal of the solvent under vacuum. The resultingsolid is dried under vacuum for several hours. The product is extracted with pentane and filtered. The pentane is removed from the filtrate under vacuum leaving the complex as a yellow solid.

B. Preparation of Borane Activator. Tris(pentafluoror)henyl)borane.
The borane activator (component (b)) was prepared by the reaction of the Grignard reagent C6FsMgBr with BF3 etherate in diethylether. After the reaction was complete, the ether solvent was removed under vacuum, the product extracted with Isopar E, the extracts filtered to yield a solution of the borane for use as component (b).

C. Preparation of Silica-Aluminoxane A 500 mL flask was charged with S.Og of SiO2 (Davison(É~ Syloid 245), which had been dehydroxylated in a fluidiæd bed in nitrogen at 600 C for 12 hours. A volume of hydrocarbon solvent, Isopar E, was then added to the silica to generate a slurry. A sample of 20 mL of a 6.2 weight percent solution of modified methylaluminoxane (Akzo Chemical) in heptane was slowly added to the slurry by syringe over the course of about 5 minutes. The result~nt mixture was heated at WO 94/07928 2 1 ~ 6 ~ 1 2 PCr/US93/09377 about 75 C for about 3 hours under nitrogen, followed by cooling to room temperature. ~

The flask was next transferred to an inert atmosphere box (nitrogen atmosphere) and the solid in the flask collected on a me~ium porosity fritte andwashed with Isopar E. After drying under nitrogen gas, the result~nt white solidwas transferred to an 8 oz. bottle and suspended in about 250 mL Isopar E
solvent. The suspension was found to contain a silica concentration of 20 g/L and an all~minum content of 0.100 M. The ratio of aluminum to silica in the sample was determined to be 5.0 mmole/g (Al:SiO2).

D. Formation of the Supr~orted Homo~eneous Catalyst Complex The (tert-butylamido)dimethyl(tetramethyl-5-cyclo-pentadienyl)silane dimethyltit~nium complex was dissolved in Isopar E to give a clear solution of Ti concentration of 5 mM. Fifty mL of this solution (0.25 mmole Ti) was added to 150 mL of the above-described slurry of silica-aluminoxane in a 16 oz. bottle and the solution was stirred for about 70 hours. The sllpern~t~nt fluid was decantedfrom the solids to remove any unsupported compounds. The solids were then resuspended in 65 mL of Isopar E. The solids were ~etPrminPd to contain 0.054 mmole Ti/g SiO2.

E. Calalyst Activation A sample of the above reaction mixture cont~ining 0.005 mmol Ti was - 25 transferred to a 4 oz bottle. The slurry was treated with 2.0 mL of component (b) from above (0.020 mmol component (b)) for 2 minlltPs at 25 C with stirrin~, and - 3g -W0 94/07928 ~ 6a~ Pcr/US93/09377 the reaction product cont~ining the activated, supported homogeneous catalyst complex slurried in the liquid hydrocarbon was transferred by syringe to the catalyst injection port on a batch polymPri7~tion reactor.

F.xample 2 Solution Polvmerization A stirred, one gallon (3.79 L) autoclave reactor was charged with two liters of Isopar E and 175 mL of octene-1, before heating to reaction temperature. The reactor was then charged with 4 mmol hydrogen gas followed by ethylene sufficient to bring the total pressure in the reactor to 450 psig. The slurry of the activated catalyst, as prepared in Example 1, was next injected into the reactor. The reaction temperature and pressure were kept essentially constant at 120 C and 450 psig, by continu~lly feeding ethylene during the polymerization reaction and cooling the reactor as nece.SS~ry. The rate and duration of the reaction were monitored by measuring the demand flow of ethylene to the reactor for the polymerization. The yield was about 235 g polyethylene (47,000 g polyethylene/mmol Ti added to the reactor) based on the amount of polymer isolated from the polymerization solution. The copolymer had a melt index of 3.4, an Ilo/I2 ratio of 6.5, and a density of 0.9084 g/cc.

F.xample 3 Slun~ Polymerization A 5 L autoclave reactor was charged with about 1850 g anhydrous hexane with stirring and the reactor contents heated to about 85 C. The reactor pressure WO 94/07928 2 ~ ~ 6 9 1. 2 PCr/US93/09377 was then increased by 5 psig by the addition of hydrogen gas to the reactor headspace, followed by a sufficient quantity of ethylene to raise the total pressure to 175 psig. A sample of activated catalyst complex containing about 0.002 mmol Ti,prepared essentially according to Example 1, was next added to the reactor through a pressurized addition cylinder. Ethylene was supplied to the reactor continuously using a demand feed regulator on the feed line. After about 45 minutes, the ethylene was blocked in and the reactor vented and cooled. The reactor contents were padded to a filter system where the polymer was removed from the hexane and dried under vacuum overnight. The yield of free-flowing, granular polyethylene thus obtained weighed 38.4 g and the product showed a melt flow rate (I2) of 0.70 g/10 min and a melt flow rate (Ilo) of 4.68 g/10 minutes.

Example 4 A. Catalyst Preparation The organometallic complex and borane activator were prepared essP.nti~lly as set forth in the Example above. The supported homogeneous catalyst was prepared as follows:
A 500 mL flask was charged with about 50 mL of toluene and about 5.0 g of SiO2 (Davidson Syloid 245), that had been dehydroxylated at about 600 C for about 12 hours in a fluidiæd bed under nitrogen. Fifty mL of methyl~ minoxane (0.991 M aluminum; 50 mmol Al) were slowly added by syringe into the slurry 25 with stirring. The reslllt~nt mixture was then heated for about 3 hours at 60 C
under a nitrogen atmosphere, after which the mixture was cooled to room WO 94/07928 PCr/US93/09377 21~Q12 temperature. The flask was then transferred to an inert atmosphere box (nitrogen) and the solid collected on a medium porosity fritte and washed 3 times with 30 mL
toluene followed by 5 washes with Isopar E. After drying under nitrogen, the white solid was transferred to an 8 oz. bottle and suspended in about 200 mL
Isopar E. The suspension was determined to contain silica at about 25 g/L and the al~lminl-m content was found to be about 0.063 M.

A sample of the above reaction mixture cont~ining a known amount of aluminum was transferred to a 4 oz. bottle, The slurry was treated with an Isopar E
solution of catalyst complex (component (a)) containing a specified amount of Tiand component (c) containing a specified amount of borane. The activation reaction was carried out essentially as described above, after which the reaction product was transferred by syringe to the catalyst injection port on the polymerization reactor.

Examples S to 15 - Solution Polyme,~izations The solution polymerization were carried out essen~i~lly as described in Example 2 above, with the exception that the reactor was charged with 150 mL
octene-l and 10 mmol hydrogen, and the components in Example 4 were used.
Table 1 summ~i7Ps the polymeri7~tion reaction conditions and certain cl~ P. ;~ilics of the polyethylene product obtained. Additionally, in reaction 12, the reactor was charged with 300 mL octene- 1 and no hydrogen was added, and in Fy~mple 13, only 4 mmol of hydrogen was charged into the reactor. Furthermore, in F.x~mlnle 14 the supported homogeneous catalyst complex was (tert-butylamido)dimethyl(tetramethyl-5-cyclopentadienyl)silane dibenzylli~;1niln,- InExample 15, the supported homogeneous catalyst complex was the WO ~4/07928 2 1 4 6 13 i 2 Pcr/l 593/09377 tetrahydroindenyl derivative (CgH 1 o-Me2Si-N-t-Bu)Ti(CH3)2.

Example 6 is a comparative example without a boron activator.

Example Reactorrl B Al Yield I2 Ilo/I2Density No. Temp. (m (m (m (g) (g/cc) (C) mol) mol) mol) 120 5 10 63 176 2.76 6.140.9121 7 120 5 10 32 135 5.97 5.850.9094 8 120 5 10 95 278 5.82 6.120.9099 9 120 5 10 126 345 6.69 6.300.9083 120 5 10 158 325 7.26 6.210.9090 11 120 5 10 126 260 6.43 6.410.9062 12 120 5 10 126 310 5.61 7.350.8785 13 120 5 10 126 288 2.60 6.740.9048 14 120 5 10 126 212 2.97 6.030.9077 120 5 10 126 233 1.5 1 6.940.8882 Example 16 - Catalyst Preparation Solutions of the Ti organometallic complex component (a) and the borane activator component (b) were prepared es.centi~lly as described in Example 1.

Component (c). A 500 mL flask was charged with 5.0 g SiO2 (Davidson 952 Silica, dehydroxylated at about 600C for greater than 18 hours) and 50 mL Isopar E. To this stirred slurry was added slowly by syringe 20 mL of a 6.2 weight percent solution of modified methylaluminoxane (Akzo Chemical) in heptane dissolved in 30 mL Isopar E. The resulting mixture was next heated at about 75 C
for about 3 hours under nitrogen, and subsequently cooled to room temperature.
The flask was transferred to an inert atmosphere (nitrogen) box and the solid WO 94/07928 Pcr/US93/09377 ~&~2 collected on a medium porosity fritte and washed with Isopar E. After dryingunder nitrogen, the white solid was transferred to an 8 oz. bottle and suspended in about 250 mL Isopar E solvent. The suspension was determined to contain a silica concentration of about 20 g/L and an aluminum content of about 0.065 M. The ratio of ~lumin~lm to silica in the sample was about 3.0 mmol AVg SiO2.

Catalyst Activation. A sample of the preceding SiO2-~lllminoxane reaction product cont~ining a known amount of Al was transferred to a 4 oz. bottle. The slurry was treated with an Isopar E solution of component (a) containing a specified amount of Ti and component (b) containing a specifled amount of borane. The activated, supported organometallic catalyst complex was transferred to a polymerization reactor via syringe injection through a catalyst injection port.

Examples 17 to 19 - Solution Polymerizations The following polymerizations were conducted according to the procedure set forth in Example 2, with the exception that the reactor was charged with 150 mL
octene and the components in Example 16 were employed. The reaction conditions and cl~ e~ Lion of t'ne ethylene-octene copolymers produced are sllmm~ri7Pd in Table 2.

Example Reactor rl B Al Yield I2 Ilo/I2 Density No. Temp. (m (m (m (g) (glcc) (C) mol) mol) mol) 17 140 5 10 65 102 2.44 5.79 0.9085 18 140 5 10 65 65 1.44 5.65 0.9124 19 140 5 10 65 1 10 1.90 5.93 0.9093 W O 94/07928 2 1 4 ~ O 1 2 PC~r/US93/09377 Example 20. Catalyst Preparation Solutions of the Ti org~nomet~llic complex component (a) and the borane activator component (b) were prepared essentially as described inExample 1.

A 100 mL flask was charged with 1.0 g of SiO2 (Davison Syloid 245, dehydroxylated at 600C) and 20 mL of Isoparaffln 2025 (an isoparaffinic hydrocarbon solvent available from Shell Chemi~l). Five mL of MMAO in heptane (8.6 wt% Al, Modified Methylaluminoxane from Akzo, Type 3A) dissolved in 10 mL of Isoparaffin 2025 was added slowly, by syringe, to the stirred SiO2 slurry. The mixture was heated to 75C for 3 hours then cooled to room temperature and allowed to stir overnight. The solid was collected on Whatman 541 filter paper and washed with an additional 10 mL of Isoparaffin 2025. The solid was not taken to complete dryness. The wet solid was transferredto a 4 oz. bottle and suspended in 50 mL of Isoparaffin 2025.

Ten mL of this solution of component (a) was added to the silica slurry and the mixture was stirred for 48 hours. After this time, the slurry was allowed tosettle and the supç-n~t~nt was removed from the soLids using a pasteur pipette. The solids were reconctitutçd to a total volume of 50 mL with Isoparaffin 2025.

The catalyst was activated by adding a solution of component (b) Cont~ining 0.2 mmol of (FsC6)3B to the slurry and stirring vigorously overnight.

Exam~le 21. Gas Phase Polymerization WO 94/07928 Pcr/US93/09377 ~ 4~al2 A one-liter cylindrical reactor specifically designed for gas phase polymçri7~tions was charged with 30 g of Teflon powder (450 micron) to act as a support bed. The reactor was then sealed and placed under vacuum at 90 C for 18 h. The reactor was cooled to 70 C and filled with nitrogen to a pressure of 20 psig. The Teflon bed was agitated at about 400 rpm and a 4 mL volume of 0.050 M MMAO in heptane was injected into the reactor by syringe. After about one minute, 1.5 cc of the activated catalyst of Example 20 was injected into the reactor from a syringe. Ethylene was then slowly added to the reactor to give an ethylene partial pressure of 200 psig and the pressure m~in~:~ined at the total pressure by feeding ethylene on demand. After 3 hours, the ethylene was blocked in and the reactor and its contents cooled to room temperature. The granular polyethylene product was removed from the reactor and weighed, giving a yield of 52.4 g of polyethylene. The product was analyzed by GPC and found to have an Mn value of 1,320,000.

Example 22. Catalyst Preparation.

A. Preparation of (Tert-hutylamido)dimethylrtetramethyl-n5-cvclo-pentadienyl)silane 2-(dimethylamino)benzyl titanium(m) Catalyst Complex.
The complex (tert-butylamido)dimethyl(tetramethyl-n5cyclo-pent~iPnyl)silanetitaniumr~m) chloride was prepared in tetrahydrofuran accordingto Example 1. This complex was treated with one equivalent of the lithium salt of dimethylaminotoluene at room temperature for 30 minl~tf s The solvent was evaporated and the solid residues extracted with pentane and the extracts filtered to remove salt by-products. The pentane solvent was removed from the extract filtrate ~ 214~1 2 W O 94/07928 PC~r/US93/09377 to yield the desired tit~nillm(m) complex.

~. Preparation of the Supported Homo~eneous Catalyst Complex.

A supported catalyst complex was prepared substantially as in Example 1 except that the silica had been dehydroxylated at 800 C for 8 h and the titanium(III) complex above was used as the organometallic compound. The final catalyst component slurry contained a Ti concentration of 1.25 millimolar.

C. Catalyst Activation.

An activated catalyst complex was formed by mixing, in a 4 oz bottle, 3.2 mL
of the catalyst component slurry prepared above and 1.2 mL of a solution of the borane activator from Example l(b) at room temperature for 3 min.
Example 23. Solution Polymerization The catalyst prepared in Example 22 was employed in a ethylene octene- 1 copolymerization under solution process conditions similar to those described inFY~mple 2 except that the reactor tP.mpe,~ was m~int~inPd at 140 C during the polymerization. The ethylene-octene- 1 copolymer recovered from the polymerization reaction weighed 236 g (59,000 g polyethylene/mmol Ti), had a melt index of 1.2, an ratio I1otI2 of 6.8, and a density of 0.9072 gtcc.

~1~60 iæ
WO 94/07928 PCr/US93/09377 Example 24. Catalys~ Preparation.

The titanium complex and the silica-aluminoxane mixture were prepared as described in Example 1. The borate activator mixture was prepared as a slurry bysuspen~ing [N,N-dimethyl~nilint-im]Etetrakis(perfluorophenyl)borate] in Isopar Ein an amount of 0.01 moles/liter. The supported homogeneous catalyst complex prepared in Example lD was activated by mixing 5.0 mL of the reaction product from Example lD with (0.005 mmol B) with this borate activator mixture and stirring at 25C for lO minutes.
~xample 25. Solution Polymerization The polymerization was conducted e~cenli~lly as set forth in Example 2 except that the reaction temperature was kept at 140C. The yield was about 197 g polyethylene (39,400 g polyethylenelmmol Ti added to the reactor) based on the amount of polymer isolated from the polymeri7~tion solution. The polymer had a melt index of 5.8, an Ilo/I2 ratio of 7.4, and a density of 0.9125 g/cc.

Claims (15)

WHAT IS CLAIMED IS:

1. An activated, supported homogeneous catalyst complex suitable for homopolymerizing ethylene or copolymerizing ethylene with at least one C3 to C18 -olefin monomer to form an ethylene polymer having a narrow molecular weight distribution, said catalyst complex comprising:

(a) an organometallic complex of the formula I:

wherein:
M is a metal of Group 4 of the Periodic Table of the Elements, Cp* is a cyclopentadienyl group bound in a n5 bonding mode to M or such a eyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amine, and mixtures thereof, said substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together cause Cp* to have afused ring structure;
Z' is a divalent moiety other than a cyclopentadienyl group or substituted cyclopentadienyl group, said moiety having up to 20 non-hydrogen atoms;

X independently each occurrence is an anionic ligand group having up to 50 non-hydrogen atoms and X is not a cyclopentadienyl or substituted cyclopentadienyl group; and n is 1 or 2 depending on the valence of M;
(b) a compound or complex capable of converting the organometallic complex (a) into a cationic complex of the formula II:

A-wherein:
Cp*, Z', M, X, and n are as defined above, and A- is a monovalent, noncoordinating, compatible anion, and (c) a catalyst support in contact with (a) and (b), said catalyst support comprising silica reacted with a methylaluminoxane, a modified methylaluminoxane, or a mixture thereof.

2. The catalyst according to Claim 1 characterized in that Z' comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur or oxygen,

3. The catalyst according to Claim 1 characterized in that M is titanium, zirconium or hafnium; X is a monovalent ligand group of up to 30 nonhydrogen atoms, and n is 1 or 2.

4. The catalyst according to Claim 2 wherein X is a C1-20 hydrocarbyl group.

5. The catalyst of Claim 1, wherein said catalyst complex comprises:

a) a coordination complex corresponding to the formula:

wherein R' each occurrence is independently selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amine, and mixtures thereof, said substituent having up to 20 non-hydrogen atoms, or optionally, twohydrocarbyl substituents together cause Cp* to have a fused ring structure a divalent derivative thereof;
X each occurrence independently is an anionic ligand group selected from the group consisting of hydride, halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide, siloxy, and combinations thereof having up to 20 non-hydrogen atoms.
Y is a divalent ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M
through said nitrogen, phosphorus, oxygen or sulfur;

M is a Group 4 metal, Z is SiR*2, CR*2, SiR*2SiR*2, CR*2CR*2, CR*=CR*, CR*2SiR*2, GeR*2 or BR;
R* each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or more R* groups from Y, Z, or from Z together with Y forms a fused ring system; and n is 1 or 2; and b) an activating cocatalyst containing a single boron atom.

6. The catalyst according to Claim 5 wherein Y is -O-,-S-,-NR*-, -PR*-and R' is independently a C1-10 hydrocarbyl group.

7. The catalyst according to Claim 5 wherein the activating cocatalyst is an alkylcycloborane, trisperfluorophenylborane or a mixture thereof.

8. The catalyst composition according to Claim 1, wherein said aluminoxane is methylaluminoxane.

9. The catalyst composition according to Claim 1, wherein said aluminoxane is modified methylaluminoxane.

10. The catalyst composition according to Claim 1, wherein the modified methylaluminoxane is the formula:

(R4X(CH3)yAlO)n wherein R4 is a linear, branched or cyclic C3 to C10 hydrocarbyl, x is from 0 to 1, y is greater than 1, and n is an integer of from 3 to 25.

11. The catalyst support according to claim 9, wherein R4 is a linear or branched C3 to C9 hydrocarbyl, x is from 0.15 to 0.50, y is froM 0.85 to 0.5 and n is an integer of from 4 to 20.

12. The catalyst support according to claim 10, wherein R4 is selected from isobutyl, tertiary butyl and n-octyl, x is from 0.2 to 0.4, y is from 0.8 to 0.6 and n is an integer of from 4 to 15.

13, A process for polymerizing an olefin, diolefin, or mixture thereof comprising contacting an olefin, dioletin, or mixture thereof with a catalyst composition according to any of the preceding Claims 1-9 under polymerization reaction conditions to polymerize said olefin, diolefin, or mixture thereof, and recovering the resulting polymer.

14. A process for preparing a supported catalyst composition comprising the steps of:

(a) preparing a organometallic complex of the formula I:

wherein:
M is a metal of Group 4 of the Periodic Table of the Elements, Cp* is a cyclopentadienyl group bound in an 5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amine, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;

Z' is a divalent moiety other than a cyclopentadienyl group or substituted cyclopentadienyl group, said moiety having up to 20 non-hydrogen atoms;

X independently each occurrence is an anionic ligand group having up to 50 non-hydrogen atoms and X is not a cyclopentadienyl or substituted cyclopentadienyl group; and n is 1 or 2 depending on the valence of M;
(b) reacting (a) with a compound or complex capable of converting the organometallic complex (a) into a cationic complex of the formula II:

15. A process for preparing a supported catalyst composition comprising the steps of:

(a) preparing a organometallic complex of the formula I:

wherein:
M is a metal of Group 4 of the Periodic Table of the Elements, Cp* is a cyclopentadienyl group bound in an 5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amine, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure;
Z' is a divalent moiety other than a cyclopentadienyl group or substituted cyclopentadienyl groups, said Z' comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 20 non-hydrogen atoms, and optionally Cp* and Z' together form a fused ring system;
X independently each occurrence is an anionic ligand group having up to 50 non-hydrogen atoms and X is not a cyclopentadienyl or substituted cyclopentadienyl group; and n is 1 or 2 depending on the valence of M;
(b) reacting (a) with a compound or complex capable of converting the organometallic complex (a) into a cationic complex of the formula II:

A-wherein:
Cp*, Z', M, X, and n are as defined with respect to previous formula I, and A-is a monovalent, noncoordinating, compatible anion, and (c) contacting the product of (b) with a catalyst support comprising silica reacted with a methylaluminoxane, a modified methylaluminoxane, or a mixture thereof.